CN103451849B - Nano-silver-containing polybutylene succinate nanofiber membrane and preparation method and application thereof - Google Patents

Abstract

The invention discloses a nano-silver-containing poly (butylene succinate) nanofiber membrane as well as a preparation method and application thereof; the nanofiber membrane has good biocompatibility, biodegradability, excellent mechanical and processing properties, and also has strong, broad-spectrum and long-acting antibacterial properties; the poly (butylene succinate) nanofiber membrane containing the nano silver is obtained by taking PBS as a base material, taking polyvinylpyrrolidone (PVP) as a stabilizer and a reducing agent, reducing silver nitrate into nano silver particles in an ethanol solution, and loading the nano silver particles in nano fibers of the PBS through electrostatic spinning, and can be used for wound dressings, antibacterial filter membranes and medical devices.

Description

Polybutylene succinate nanofiber film containing nano silver and its preparation method and application

technical field

The invention belongs to the field of nanofibers, and in particular relates to a polybutylene succinate nanofiber film containing nanosilver and a preparation method and application thereof.

Background technique

Nano-silver with a diameter of 1-100nm has more stable physical and chemical properties, higher surface activity and lower toxicity in vivo than conventional silver. In terms of antibacterial applications, due to the small size effect quantum effect and large specific surface area, nano silver has a stronger antibacterial effect than traditional inorganic antibacterial agents, and silver elements will not cause bacteria to develop drug resistance. Introducing silver nanoparticles into In polymer nanofibers, effective anti-infection properties can be endowed to the fibers, thereby further expanding their application range in the biomedical field.

The preparation of polymer nanofibrous membranes loaded with silver nanoparticles by electrospinning technology has become a hot issue that researchers have paid close attention to recently. This nanocomposite combines the unique properties of nanosilver particles with the excellent properties of polymer nanofibers. Electrospun polymer nanofiber membranes have special properties such as large specific surface area and high porosity, and have broad application prospects in biomedical fields such as tissue engineering scaffolds, skin repair, and wound dressings.

The preparation of the existing composite fiber of nano-silver particle and polymer includes four ways.

The first is to directly disperse nano-silver particles in polymer solution, and perform electrospinning to obtain composite fibers. The advantage of this method is that it is not limited by the common solvent and polymer chemical structure, and it can choose a variety of different solvents and polymers. However, this method has the problem that nanoparticles are prone to agglomeration. In existing literature, CN101077473 avoids agglomeration by adding an ultrasonic device, but this will increase equipment costs.

The second is to directly dissolve silver ions (usually nitrate powder) in the polymer solution for electrospinning, and then reduce the silver ions in the solution or in the fiber to elemental silver in situ by physical or chemical methods, thereby uniform distribution of silver nanoparticles in the fiber. For example CN101096424. The advantage of this approach is that it is less constrained by common solvents and polymer chemistry. However, this method has the problems of complicated preparation process and harsh preparation conditions. For example, CN101096424 needs to adopt ultraviolet light irradiation to carry out photoreduction of silver nitrate.

The third is to directly attach nano-silver particles to surface-treated polymer fibers. The advantage of this approach is that it is not limited by common solvents and polymer chemical structures. However, the adhesion effect is highly required by the adhesion conditions, and the surface treatment of polymer fibers is complicated.

The fourth is to use the in situ generation of silver nanoparticles during the electrospinning process. However, this requires the selection of a co-solvent for the polymer and the silver ions, the co-solvent needs to have good compatibility, and the polymer needs to have specific chemical groups that can interact strongly with the silver atoms.

Polybutylene succinate (PBS) is a new type of biodegradable aliphatic polyester, which has good degradability, biocompatibility, mechanical properties, processability and other advantages, and compared with PLGA, PGA, PLA, etc., the production cost of PBS is relatively low. Relevant studies have shown that PBS can be used as a potential biomaterial in biomedical fields such as tissue engineering and drug release. Suttiphong prepared PBS nanofiber nonwovens by electrospinning technology and studied its potential as tissue engineering materials. Due to the unique properties of PBS nanofiber nonwovens - high porosity, microporous structure and large specific surface area, compared with ordinary films, nanofiber nonwovens are less effective for the adhesion of osteoblasts (SaOs-2) on the material. Attachment, growth and activity have obvious promoting effect. But so far, the preparation of PBS composites containing nano-silver by electrospinning has not been reported.

In summary, there is a need for a new method for preparing polybutylene succinate nanofiber membranes containing nanosilver, which can avoid the agglomeration of silver particles without the intervention of an external field, and has simple steps and low condition requirements.

Contents of the invention

The first technical problem to be solved in the present invention is to provide a polybutylene succinate nanofiber membrane containing nano-silver; the nanofiber membrane has good biocompatibility, biodegradability, excellent mechanics and processing properties , but also has strong, broad-spectrum and long-lasting antibacterial properties.

The second technical problem to be solved in the present invention is to provide the preparation method of the polybutylene succinate nanofiber film containing nano-silver; , silver nitrate was reduced to nano silver particles in ethanol solution, and nano silver particles were loaded in PBS nanofibers by electrospinning to obtain polybutylene succinate nanofiber membranes containing nano silver.

The third technical problem to be solved by the present invention is to provide the application of polybutylene succinate nanofiber membrane containing nano-silver, which can be used for wound dressings, antibacterial filter membranes, and medical devices.

In order to solve the problems of the technologies described above, the present invention provides a polybutylene succinate nanofiber film containing nano-silver, which is composed of nano-silver and polybutylene succinate fibers, and the nano-silver particles are evenly distributed on the polybutylene succinate. Butylene glycol ester fibers, wherein the diameter of the fiber is 50-500nm, and the diameter of the nano-silver particles is 2-15nm.

The polybutylene succinate has a melting point of 110-120° C. and a molecular weight of 50,000-200,000.

For solving the problems of the technologies described above, the invention provides the preparation method of the polybutylene succinate nanofiber film containing nano-silver, comprising the following steps:

1) Preparation of nano silver:

Mix the ethanol solution of silver nitrate and the ethanol solution of polyvinylpyrrolidone, and stir until the color of the solution changes from colorless and transparent to deep red, and does not change any more, so as to obtain the ethanol solution containing nano-silver particles;

2) Electrospinning of polybutylene succinate fiber membrane containing nano-silver:

Polybutylene succinate is dissolved, and the ethanol solution containing nano-silver particles obtained in step 1) is added in the polybutylene succinate solution, after stirring evenly, electrospinning is carried out, and nanowires are received to obtain Polybutylene succinate nanofibrous film containing nanosilver.

Further, the concentration of the ethanol solution of silver nitrate in the step 1) is 0.001-0.03 g/ml.

Further, the concentration of the ethanol solution of polyvinylpyrrolidone in the step 1) is 0.02-0.2 g/ml.

Further, in the step 1), the ethanol solution of silver nitrate and the ethanol solution of polyvinylpyrrolidone are mixed, heated and stirred at 40-60°C.

Further, the volume ratio of the ethanol solution containing nano-silver particles to the chloroform solution of PBS in the step 2) is 0.01-0.25.

Further, the electrospinning process parameters in the step 2) are as follows: voltage 15-30KV, receiving distance 10-20cm, spinning cavity inner diameter 0.2mm-0.8mm, spinning speed 30-80ul/min.

In the step 2), the nanowires are received by aluminum foil or stainless steel support.

Step 2) The prepared nanofibrous membrane can be stored at room temperature and vacuum-dried.

In order to solve the above technical problems, the present invention provides the application of polybutylene succinate nanofiber membrane containing nano silver, which can be used as wound dressing, antibacterial filter membrane and medical device.

The advantages of the present invention are:

The present invention utilizes the unique chemical structure of polyvinylpyrrolidone (PVP). When preparing nano-silver particles, PVP can reduce silver ions on the one hand, and can evenly cover the surface of the reduced silver particles to act as a stabilizer. The preparation process is simple. , easy to operate, and the obtained nano-silver particles are uniform in size and small in particle size;

The nanofiber membrane prepared by the electrospinning method of the present invention can attach the pre-prepared nano silver particles to the nanofiber in one step, and is not limited by the co-solvent and the chemical structure of the polymer, and has strong applicability;

The present invention uses nano-silver particles, its small size effect, quantum effect and huge specific surface area have stronger antibacterial effect than traditional inorganic antibacterial agents, so that the prepared nanofiber membrane can be used as wound dressings, antibacterial filter membranes, medical devices, etc.

Description of drawings

Fig. 1 is the scanning electron micrograph of the nano-silver/PBS fiber film that embodiment 1 makes;

Fig. 2 is the transmission electron microscope figure of the nano-silver/PBS fiber film that embodiment 1 makes;

Fig. 3 is the scanning electron micrograph of the nano-silver/PBS fiber film that embodiment 2 makes;

Fig. 4 is the transmission electron micrograph of the nano-silver/PBS fiber film that embodiment 2 makes.

detailed description

The present invention will be further described below in conjunction with the embodiments and accompanying drawings.

Example 1

The preparation method of the polybutylene succinate nanofiber membrane containing nanometer silver, comprises the following steps:

Weigh 0.03 grams of silver nitrate and 0.5 grams of PVP and dissolve them in 10ml ethanol solution, stir until completely dissolved, quickly add the ethanol solution of silver nitrate to the ethanol solution of PVP, and heat to 50°C at the same time, stir evenly, until the solution color From colorless and transparent to deep red, and no longer change, stable nano-silver particles are obtained;

Weigh 0.6 g of PBS and dissolve it in 4 ml of chloroform solution, stir until the PBS is completely dissolved; take 1 ml of the above-prepared ethanol solution of silver nanoparticles and add it to the chloroform solution of PBS, stir until the solution is evenly mixed, and then carry out electrospinning after standing. The voltage is 20KV, the advancing speed of the syringe pump is 50ul/min, the receiving distance is 15cm, the diameter of the spinneret hole is 0.5mm, and the aluminum foil is used to receive the electrospun PBS nanofiber membrane containing nano-silver, which is vacuum-dried for 24 hours and sealed for storage .

The average diameter of the fiber is 450nm, and the average diameter of the nano-silver particles is 5nm.

Fig. 1 is the scanning electron micrograph of the nano-silver/PBS fiber film that embodiment 1 makes.

Fig. 2 is the transmission electron micrograph of the nano-silver/PBS fiber membrane that embodiment 1 makes.

Example 2

The preparation method of the polybutylene succinate nanofiber membrane containing nanometer silver, comprises the following steps:

Weigh 0.12 grams of silver nitrate and 0.5 grams of PVP and dissolve them in 10ml ethanol solution, stir until completely dissolved, quickly add the ethanol solution of silver nitrate to the ethanol solution of PVP, and heat to 50°C at the same time, stir evenly, until the solution color From colorless and transparent to deep red, and no longer change, stable nano-silver particles are obtained at this time.

Weigh 0.6 g of PBS and dissolve it in 4 ml of chloroform solution, stir until the PBS is completely dissolved; take 1 ml of the above-prepared ethanol solution of silver nanoparticles and add it to the chloroform solution of PBS, stir until the solution is evenly mixed, and then carry out electrospinning after standing. The voltage is 20KV, the advancing speed of the syringe pump is 50ul/min, the receiving distance is 15cm, the diameter of the spinneret hole is 0.5mm, and the aluminum foil is used to receive the electrospun PBS nanofiber membrane containing nano-silver, which is vacuum-dried for 24 hours and sealed for storage .

The average diameter of the fiber is 300nm, and the average diameter of the nano-silver particles is 8nm.

Fig. 3 is the scanning electron micrograph of the nano-silver/PBS fiber film that embodiment 2 makes.

Fig. 4 is the transmission electron micrograph of the nano-silver/PBS fiber film that embodiment 2 makes.

Example 3

The preparation method of the polybutylene succinate nanofiber membrane containing nanometer silver, comprises the following steps:

1) Preparation of nano silver:

Mix the ethanol solution of silver nitrate and the ethanol solution of polyvinylpyrrolidone, and stir until the color of the solution changes from colorless and transparent to deep red, and does not change any more, so as to obtain the ethanol solution containing nano-silver particles;

2) Electrospinning of polybutylene succinate fiber membrane containing nano-silver:

Polybutylene succinate is dissolved in chloroform, the ethanol solution containing nano-silver particles that step 1) obtains is added in the chloroform solution of polybutylene succinate, after stirring, carry out electrospinning, Receiving nano wires to obtain polybutylene succinate nanofiber membranes containing nano silver;

Wherein, the ethanol solution concentration of silver nitrate in the step 1) is 0.001g/ml; the ethanol solution concentration of polyvinylpyrrolidone in the step 1) is 0.02g/ml; the step 2) contains silver nanoparticles The volume ratio of the ethanol solution to the chloroform solution of PBS is 0.01; the electrospinning process parameters in the step 2) are as follows: voltage 15KV, receiving distance 10cm, spinning cavity inner diameter 0.2mm, spinning speed 30ul/min.

Example 4

The preparation method of the polybutylene succinate nanofiber membrane containing nanometer silver, comprises the following steps:

1) Preparation of nano silver:

Mix the ethanol solution of silver nitrate and the ethanol solution of polyvinylpyrrolidone, and stir until the color of the solution changes from colorless and transparent to deep red, and does not change any more, so as to obtain the ethanol solution containing nano-silver particles;

2) Electrospinning of polybutylene succinate fiber membrane containing nano-silver:

Polybutylene succinate is dissolved in chloroform, the ethanol solution containing nano-silver particles that step 1) obtains is added in the chloroform solution of polybutylene succinate, after stirring, carry out electrospinning, Receiving nano wires to obtain polybutylene succinate nanofiber membranes containing nano silver;

Wherein, the ethanol solution concentration of silver nitrate in the step 1) is 0.03g/ml; the ethanol solution concentration of polyvinylpyrrolidone in the step 1) is 0.2g/ml; the step 2) containing nano-silver particles The volume ratio of the ethanol solution to the chloroform solution of PBS is 0.25; the electrospinning process parameters in the step 2) are as follows: voltage 30KV, receiving distance 20cm, spinning cavity inner diameter 0.8mm, spinning speed 80ul/min.

Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. All the implementation manners cannot be exhaustively listed here. All obvious changes or variations derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims (4)

1. a preparation method of polybutylene succinate nanofiber membrane containing nano-silver, is characterized in that, may further comprise the steps: 1) Preparation of nano silver: Mix the ethanol solution of silver nitrate and the ethanol solution of polyvinylpyrrolidone, and stir until the color of the solution changes from colorless and transparent to deep red, and does not change any more, so as to obtain the ethanol solution containing nano-silver particles; 2) Electrospinning of polybutylene succinate nanofiber membranes containing nanosilver: Polybutylene succinate is dissolved in chloroform, and the ethanol solution containing nano-silver particles obtained in step 1) is added in the polybutylene succinate solution, and after stirring evenly, electrospinning is carried out, and the nanometer silver particles are received. Silk, obtain the polybutylene succinate nanofiber film containing nano-silver; The ethanol solution concentration of silver nitrate in step 1) is 0.001～0.03g/ml, and the ethanol solution concentration of polyvinylpyrrolidone is 0.02～0.2g/ml; The volume ratio of the ethanol solution containing nano-silver particles to the chloroform solution of PBS in step 2) is 0.01～0.25; Electrospinning process parameters are as follows: voltage 15-30KV, receiving distance 10-20cm, spinning hole inner diameter 0.2mm-0.8mm, spinning speed 30-80μl/min; The polybutylene succinate nanofiber film containing nano-silver is composed of nano-silver and polybutylene succinate fibers, and the nano-silver particles are distributed on the polybutylene succinate fibers, and the fiber diameter 50-500nm, and the diameter of nano-silver particles is 2-15nm. 2. the preparation method of the polybutylene succinate nanofiber membrane containing nano-silver according to claim 1, is characterized in that, the fusing point of described polybutylene succinate is 110～120 ℃, molecular weight 50,000 to 200,000. 3. the preparation method of the polybutylene succinate nanofiber film containing nano-silver according to claim 1, is characterized in that, described step 1) in the ethanol solution of silver nitrate and the ethanol solution of polyvinylpyrrolidone Stir at 40-60°C after mixing. 4. according to the application of the polybutylene succinate nanofiber film containing nano-silver prepared by the arbitrary described method of claim 1～3, it is characterized in that, it can be used as wound dressing, antibacterial filter membrane, medical device.